Process for Preparation of Hydrocracking Catalyst for Use in Hydrocracking of Hydrocarbon Streams

ABSTRACT

A process for activating and maintaining a catalyst for use in hydrocracking a hydrocarbon stream includes continuously contacting a hydrocarbon stream with a hydroprocessing catalyst in the presence of hydrogen. Sulphides and chloride compounds in the hydrocarbon stream are used such that the hydroprocessing catalyst has the ability to hydrogenate, dechlorinate, and hydrocrack components of the hydrocarbon stream.

CROSS REFERENCE TO RELATED APPLICATIONS

The present application is a continuation of and claims priority toInternational Application No. PCT/IB2016/051135 filed Mar. 1, 2016,entitled “Process for Preparation of Hydrocracking Catalyst for Use inHydrocracking of Hydrocarbon Streams,” which claims priority to U.S.Provisional Application No. 62/201,664 filed on Aug. 6, 2015, entitled“Process for Preparation of Hydrocracking Catalyst for Use inHydrocracking of Hydrocarbon Streams,” and Indian ProvisionalApplication No. 1166/CHE/2015 filed Mar. 10, 2015 entitled “Process forPreparation of Hydrocracking Catalyst for Use in Hydrocracking ofHydrocarbon Streams and Pyrolysis Oil,” which applications areincorporated by reference herein in their entirety.

TECHNICAL FIELD

The present disclosure relates to the preparation of hydrocrackingcatalysts for the treatment of hydrocarbon streams resulting frompyrolysis of waste plastics for use in downstream processes.

BACKGROUND

Waste plastics contain polyvinylchloride (PVC). Through a pyrolysisprocess, waste plastics can be converted to gas and liquid products.These liquid products contain paraffins, i-paraffins (iso-paraffins),olefins, naphthenes, and aromatic components along with organicchlorides in concentrations of hundreds of ppm. However, the liquidproducts of a pyrolysis process (pyrolysis oils) are off-spec for use asa feedstock for steam crackers because steam cracker feed specificationsrequire chloride levels less than 3 ppm, olefin content less than 1 wt%, and boiling end point requirements of 370° C.

SUMMARY

Disclosed herein is a process for activating and maintaining a catalystfor use in hydrotreating a hydrocarbon stream to simultaneously reduceheavier boiling components, chlorides, and olefins, comprisingcontinuously contacting the hydrocarbon stream with a hydroprocessingcatalyst in the presence of hydrogen, wherein the hydrocarbon streamcomprises one or more chloride compounds and one or more sulphides.

BRIEF DESCRIPTION OF THE DRAWINGS

FIG. 1 illustrates a hydroprocessing system which utilizes thehydrocracking catalyst prepared as described herein for hydrocracking,hydrogenating, and dechlorinating components of a hydrocarbon stream tolevels suitable for introduction to a steam cracker.

FIG. 2 is a graph of a staged catalyst sulphiding protocol, showingtemperature versus time.

DETAILED DESCRIPTION

Other than in the operating examples or where otherwise indicated, allnumbers or expressions referring to quantities of ingredients, reactionconditions, and the like, used in the specification and claims are to beunderstood as modified in all instances by the term “about.” Variousnumerical ranges are disclosed herein. Because these ranges arecontinuous, they include every value between the minimum and maximumvalues. The endpoints of all ranges reciting the same characteristic orcomponent are independently combinable and inclusive of the recitedendpoint. Unless expressly indicated otherwise, the various numericalranges specified in this application are approximations. The endpointsof all ranges directed to the same component or property are inclusiveof the endpoint and independently combinable. The term “X or more” meansthat the named component is present in an amount of the value X, andvalues which are more than X.

The terms “a,” “an,” and “the” do not denote a limitation of quantity,but rather denote the presence of at least one of the referenced item.As used herein the singular forms “a,” “an,” and “the” include pluralreferents.

As used herein, “combinations thereof” is inclusive of one or more ofthe recited elements, optionally together with a like element notrecited, e.g., inclusive of a combination of one or more of the namedcomponents, optionally with one or more other components notspecifically named that have essentially the same function. As usedherein, the term “combination” is inclusive of blends, mixtures, alloys,reaction products, and the like.

Reference throughout the specification to “an embodiment,”“embodiments,” “another embodiment,” “other embodiments,” “alternativeembodiments,” “additional embodiments,” “some embodiments,” and so forth(e.g., the use of “additionally” and/or “alternatively” in the contextof describing one or more embodiments), means that a particular element(e.g., feature, structure, property, and/or characteristic) described inconnection with the embodiment is included in at least an embodimentdescribed herein, and may or may not be present in other embodiments. Inaddition, it is to be understood that the described element(s) can becombined in any suitable manner in the various embodiments.

Disclosed herein are embodiments of a process for preparing ahydrocracking catalyst for use in hydrocracking hydrocarbon streams. Theembodiments involve activating and maintaining a catalyst for use inhydrocracking a hydrocarbon stream. Generally, the process includescontinuously contacting a hydrocarbon stream with a hydroprocessingcatalyst in the presence of hydrogen, where the hydrocarbon streamcomprises one or more chloride compounds and one or more sulphides. Incertain embodiments, before the step of continuously contacting thehydrocarbon stream with the hydroprocessing catalyst in the presence ofhydrogen, the process may include contacting a catalyst activatingstream with the hydroprocessing catalyst, wherein the catalystactivating stream comprises one or more sulphides.

Embodiments of the process for preparing a hydrocracking catalyst aredescribed in context with reference to FIG. 1. FIG. 1 illustrates ahydroprocessing which utilizes the hydrocracking catalyst prepared asdescribed herein for hydrocracking components of a hydrocarbon stream 1to levels suitable for introduction to a steam cracker 30. In additionalembodiments, the hydroprocessing catalyst is used for dechlorinatingchloride compounds and hydrogenating olefins contained in a hydrocarbonstream 1 to levels suitable for introduction to the steam cracker 30.

The hydroprocessing system 100 includes a hydroprocessing reactor 10, aseparator 20, and a steam cracker 30. The hydrocarbon stream 1 feeds tothe hydroprocessing reactor 10, and the reaction product effluent flowsfrom the hydroprocessing reactor 10 in the hydrocarbon product stream 2to the separator 20. In separator 20, a treated product (e.g., in gas orliquid form) is recovered from the hydrocarbon product stream 2 andflows from the separator 20 via treated hydrocarbon stream 4, with oneor more sulphur-containing gases and/or chlorine-containing gasesflowing from the separator 20 in stream 3. Embodiments of the disclosurecontemplate a second hydroprocessing reactor and a second separator maybe placed in between separator 20 and treated hydrocarbon stream 4. Thetreated product flowing from the separator 20, in such embodiments, maycontain residual sulphur, and the second hydroprocessing reactor/secondseparator combination may treat the treated product flowing from theseparator 20 to completely remove the sulphur such that a second treatedproduct flowing in the treated hydrocarbon stream 4 from the secondseparator contains less than 200, 100, 90, 80, 70, 60, 50, 40, 30, 20,10, 9, 8, 7, 6, 5, 4, 3, 2, 1, 0.5, 0.1 ppmw S based on total weight ofthe treated hydrocarbon stream 4.

The treated product in the treated hydrocarbon stream 4 may flowdirectly (e.g., without any separations or fractionations of the treatedhydrocarbon stream 4) or via blended hydrocarbon stream 4′ (e.g.,without any separations or fractionations of the treated hydrocarbonstream 4 and blended hydrocarbon stream 4′) to a steam cracker 30, fromwhich high value products flow in stream 6.

The hydrocarbon stream 1 generally includes one or more hydrocarbons, atleast a portion of which are heavy hydrocarbon molecules. Inembodiments, the hydrocarbon stream 1 may additionally include one ormore sulphides, one or more chloride compounds, hydrogen, orcombinations thereof. The hydrocarbon stream 1 is generally in a liquidphase. A hydrogen (H₂) stream can be added to hydrocarbon stream 1before entering the hydroprocessing reactor 10. Optionally, a H₂ streamis additionally added in between various catalyst beds in a multi-bedarrangement in the hydroprocessing reactor 10 to enrich the reactorenvironment with H₂.

The hydrocarbon stream 1 may be a stream from an upstream process, suchas a pyrolysis process, which contains one or more chloride compounds,and optionally, also one or more sulphides, for example, from thepyrolysis of waste plastics. In an embodiment wherein the stream fromthe upstream process does not contain the one or more sulphides, thehydrocarbon stream 1 may be doped with the one or more sulphides, via adoping stream 7.

Examples of the one or more hydrocarbons which may be included in thehydrocarbon stream 1 include paraffins (n-paraffin, i-paraffin, orboth), olefins, naphthenes, aromatic hydrocarbons, or combinationsthereof. When the one or more hydrocarbons includes all the listedhydrocarbons, the group of hydrocarbons may be collectively referred toas a PONA feed (paraffin, olefin, naphthene, aromatics) or PIONA feed(n-paraffin, i-paraffin, olefin, naphthene, aromatics). A particularembodiment of the hydrocarbon stream 1 is a plastic pyrolysis oil,discussed in more detail below.

Any paraffin may be included in the hydrocarbon stream 1. Examples ofparaffins which may be included in the hydrocarbon stream 1 include, butare not limited to, C₁ to C₂₂ n-paraffins and i-paraffins. In anembodiment, the concentration of paraffins in the hydrocarbon stream 1may be less than 10 wt % based on the total weight of the hydrocarbonstream 1. Alternatively, the concentration of paraffins in thehydrocarbon stream 1 may be 10 wt %, 20 wt %, 30 wt %, 40 wt %, 50 wt %,60 wt %, or more based on the total weight of the hydrocarbon stream 1.While embodiments include paraffins of carbon numbers up to 22, thedisclosure is not limited to carbon number 22 as an upper end-point ofthe suitable range of paraffins, and the paraffins can include highercarbon numbers, e.g., 23, 24, 25, 26, 27, 28, 29, 30, 31, 32, 33, 34,35, 36, 37, 38, 39, 40, and higher. In embodiments, at least a portionof the paraffins in the hydrocarbon stream 1 comprises at least aportion of the heavy hydrocarbon molecules.

Any olefin may be included in the hydrocarbon stream 1. Examples ofolefins which may be included in hydrocarbon stream 1 include, but arenot limited to, C₂ to C₁₀ olefins and combinations thereof. In anembodiment, the concentration of olefins in the hydrocarbon stream 1 maybe less than 10 wt % based on the total weight of the hydrocarbon stream1. Alternatively, the concentration of olefins in the hydrocarbon stream1 may be 10 wt %, 20 wt %, 30 wt %, 40 wt % or more based on the totalweight of the hydrocarbon stream 1. In embodiments, at least a portionof the one or more olefins in the hydrocarbon stream 1 comprise at leasta portion of the heavy hydrocarbon molecules. While embodiments includeolefins of carbon numbers up to 10, the disclosure is not limited tocarbon number 10 as an upper end-point of the suitable range of olefins,and the olefins can include higher carbon numbers, e.g., 11, 12, 13, 14,15, 16, 17, 18, 19, 20, 21, 22, 23, 24, 25, 26, 27, 28, 29, 30, andhigher.

In an embodiment, the hydrocarbon stream 1 comprises no olefins.

Any naphthene may be included in the hydrocarbon stream 1. Examples ofnaphthenes include, but are not limited to, cyclopentane, cyclohexane,cycloheptane, and cyclooctane. In an embodiment, the concentration ofnaphthenes in the hydrocarbon stream 1 may be less than 10 wt % based onthe total weight of the hydrocarbon stream 1. Alternatively, theconcentration of naphthenes in the hydrocarbon stream 1 may be 10 wt %,20 wt %, 30 wt %, 40 wt % or more based on the total weight of thehydrocarbon stream 1. While embodiments include naphthenes of carbonnumbers up to 8, the disclosure is not limited to carbon number 8 as anupper end-point of the suitable range of naphthenes, and the naphthenescan include higher carbon numbers, e.g., 9, 10, 11, 12, 13, 14, 15, 16,17, 18, 19, 20, 21, 22, 23, 24, 25, 26, 27, 28, 29, 30, and higher. Inembodiments, at least a portion of the naphthenes in the hydrocarbonstream 1 comprise at least a portion of the heavy hydrocarbon molecules.

Any aromatic hydrocarbon may be included in the hydrocarbon stream 1.Aromatic hydrocarbons suitable for use in the hydrocarbon stream 1include, but are not limited to, benzene, toluene, xylenes, ethylbenzene, or combinations thereof. In an embodiment, the concentration ofaromatic hydrocarbons in the hydrocarbon stream 1 may be less than 10 wt% based on the total weight of the hydrocarbon stream 1. Alternatively,the concentration of aromatic hydrocarbons in the hydrocarbon stream 1may be 10 wt %, 20 wt %, 30 wt %, 40 wt % or more based on the totalweight of the hydrocarbon stream 1. In embodiments, at least a portionof the aromatics in the hydrocarbon stream 1 comprise at least a portionof the heavy hydrocarbon molecules. While embodiments include aromatichydrocarbons of carbon numbers up to 8, the disclosure is not limited tocarbon number 8 as an upper end-point of the suitable range of aromatichydrocarbons, and the aromatic hydrocarbons can include higher carbonnumbers, e.g., 9, 10, 11, 12, 13, 14, 15, 16, 17, 18, 19, 20, 21, 22,23, 24, 25, 26, 27, 28, 29, 30, and higher. In an embodiment, thearomatic hydrocarbons carbon number is as high as 22.

In an embodiment, the hydrocarbon stream 1 comprises no aromatichydrocarbons.

As discussed herein, embodiments of the processes disclosed hereincontemplate hydrocracking of molecules, and in particular, heavyhydrocarbon molecules of the hydrocarbon stream 1. In an embodiment, theconcentration of heavy hydrocarbon molecules in the hydrocarbon stream 1may be less than 10 wt % based on the total weight of the hydrocarbonstream 1. Alternatively, the concentration of the heavy hydrocarbonmolecules in the hydrocarbon stream 1 may be 10 wt % to 90 wt % based onthe total weight of the hydrocarbon stream 1. As described above, theheavy hydrocarbon molecules may include paraffins, i-paraffins, olefins,naphthenes, aromatic hydrocarbons, or combinations thereof. Inembodiments, the heavy hydrocarbon molecules may include C₁₆ and largerhydrocarbons. Greater than 5, 10, 15, 20, 25, 30 wt % or more of theheavy hydrocarbon molecules in the hydrocarbon stream 1 is hydrocrackedwhen the hydrocarbon stream 1 is contacted with the hydroprocessingcatalyst in the hydroprocessing reactor 10.

Chloride compounds which may be included in the hydrocarbon stream 1include, but are not limited to, aliphatic chlorine-containinghydrocarbons, aromatic chlorine-containing hydrocarbons, and otherchlorine-containing hydrocarbons. Examples of chlorine-containinghydrocarbons include, but are not limited to, 1-chlorohexane,2-chloropentane, 3-chloro-3-methyl pentane, (2-chloroethyl) benzene,chlorobenzene, or combinations thereof. The concentration of chloridecompounds in the hydrocarbon stream 1 may be 5 ppm, 6 ppm, 7 ppm, 8 ppm,9 ppm, 10 ppm, 15 ppm, 20 ppm, 30 ppm, 40 ppm, 50 ppm, 100 ppm, 200 ppm,300 ppm, 400 ppm, 500 ppm, 600 ppm, 700 ppm, 800 ppm, 900 ppm, 1,000ppm, 1,100 ppm, 1,200 ppm, 1,300 ppm, 1,400 ppm, 1,500 ppm, 1,600 ppm,1,700 ppm, 1,800 ppm, 1,900 ppm, 2,000 ppm or more based on the totalweight of the hydrocarbon stream 1.

Sulphides which may be included in the hydrocarbon stream 1 includesulphur-containing compounds. For example, a sulphiding agent such asdimethyl disulphide (C₂H₆S₂), dimethyl sulphide (C₂H₆S), mercaptans(R—SH), carbon disulphide (CS₂), hydrogen sulphide (H₂S), orcombinations thereof may be used as the sulphide in the hydrocarbonstream 1.

In an embodiment, one or more sulphides (e.g., dimethyl disulphide(C₂H₆S₂), dimethyl sulphide (C₂H₆S), mercaptans (R—SH), carbondisulphide (CS₂), hydrogen sulphide (H₂S), or combinations thereof) areadded to the hydrocarbon stream 1 (e.g., the hydrocarbon stream 1 is“doped” with one or more sulphides), for example, via a doping stream 7,before the hydrocarbon stream 1 is introduced to the hydroprocessingreactor 10. In such embodiments, the one or more sulphides are added tothe hydrocarbon stream 1 in an amount such that a sulphur content of thehydrocarbon stream 1, after sulphide addition, is about 0.5 wt %, 1 wt%, 1.5 wt %, 2 wt %, 2.5 wt %, 3 wt %, 3.5 wt %, 4 wt %, 4.5 wt %, 5 wt% or more based on the total weight of the hydrocarbon stream 1. Inembodiments, the doping stream 7 may include components tailored fordoping such as hexadecane and dimethyl disulphide; alternatively, thedoping stream 7 may be a heavier oil (e.g., naphtha, diesel, or both)which already contains sulphide compounds (or to which sulphides aredoped to achieve the sulphur content disclosed herein) and which isblended with the hydrocarbon stream 1 to achieve the sulphur contentdescribed above.

In alternative embodiments, one or more sulphides are present in thehydrocarbon stream as a result of upstream processing from which thehydrocarbon stream 1 flows. In such embodiments, the hydrocarbon stream1 may contain one or more sulphides in an amount such that a sulphurcontent of the hydrocarbon stream 1, without sulphide doping, is about0.5 wt %, 1 wt %, 1.5 wt %, 2 wt %, 2.5 wt %, 3 wt %, 3.5 wt %, 4 wt %,4.5 wt %, 5 wt % or more based on the total weight of the hydrocarbonstream 1.

In yet other embodiments, the hydrocarbon stream 1 may contain one ormore sulphides in an amount insufficient for sulphiding (e.g., less than5,000, 4,000, 3,000, 2,000, 1,000, 900, 800, 700, 600, 500, 400, 300,200, 100, 90, 80, 70, 60, 50, 40, 30, 20, 10, 5, or 1 ppm) thehydroprocessing catalyst contained in the hydroprocessing reactor 10(the catalyst is discussed in more detail below), and doping stream 7 isutilized to raise the concentration of the one or more sulphides in thehydrocarbon stream to such that a sulphur content of the hydrocarbonstream 1, after sulphide addition, is about 0.5 wt %, 1 wt %, 1.5 wt %,2 wt %, 2.5 wt %, 3 wt %, 3.5 wt %, 4 wt %, 4.5 wt %, 5 wt % or morebased on the total weight of the hydrocarbon stream 1.

In an embodiment, the sulphur content of the hydrocarbon stream 1, aftersulphide addition using doping stream 7, is up to about 3 wt % based onthe total weight of the hydrocarbon stream 1. In another embodiment, thesulphur content of the hydrocarbon stream 1, without sulphide additionusing doping stream 7, is up to about 3 wt % based on the total weightof the hydrocarbon stream 1.

In embodiments, the hydrocarbon stream 1 may be one or more pyrolysisoils which contain any of the paraffins, i-paraffins, olefins,naphthenes, aromatic hydrocarbons, chloride compounds, sulphides, orcombinations thereof as disclosed herein. The one or more pyrolysis oilsmay be obtained from pyrolysis of waste plastics (for example, from ahigh severity process as disclosed in U.S. Pat. No. 8,895,790, which isincorporated by reference in its entirety, or from any low temperatureseverity pyrolysis process known in the art with the aid of thisdisclosure). It is contemplated that for embodiments having one or moreplastic pyrolysis oils in the hydrocarbon stream 1, at least a portionof the plastic pyrolysis oils comprises heavy hydrocarbon molecules(e.g., also referred to as heavy ends of the pyrolysis oils).Hydrocracking of the heavy ends of the plastic pyrolysis oils to meetsteam cracker 30 specifications is contemplated.

Other streams which may comprise at least a portion of the hydrocarbonstream 1 include a reformate stream from catalytic naphtha reformer,tire pyrolysis oil, and any other chloride containing hydrocarbonstream.

In embodiments, the hydrocarbon stream 1 may be one or more pyrolysisoils as described above which is blended with a heavier oil (e.g., anaphtha or diesel, via doping stream 7). In such embodiments, blendingthe treated hydrocarbon stream 4 with a non-chlorinated stream 5 asdescribed for embodiments below may additionally occur; alternatively,the subsequent blending may not occur.

The hydroprocessing reactor 10 is configured to hydrocrack, and in someembodiments, additionally dechlorinate and hydrogenate components of thehydrocarbon stream 1 fed to the hydroprocessing reactor 10. In thehydroprocessing reactor 10, the hydrocarbon stream 1 is contacted withthe hydroprocessing catalyst in the presence of hydrogen to yield ahydrocarbon product in stream 2. It is contemplated the hydrocarbonstream 1 may be contacted with the hydroprocessing catalyst in upwardflow, downward flow, radial flow, or combinations thereof, with orwithout a staged addition of hydrocarbon stream 1, doping stream 7, a H₂stream, or combinations thereof. It is further contemplated thecomponents of the hydrocarbon stream 1 may be in the liquid phase, aliquid-vapor phase, or a vapor phase while in the hydroprocessingreactor 10.

The hydroprocessing reactor 10 may facilitate any reaction of thecomponents of the hydrocarbon stream 1 in the presence of, or with,hydrogen. Reactions may occur as the addition of hydrogen atoms todouble bonds of unsaturated molecules (e.g., olefins, aromaticcompounds), resulting in saturated molecules (e.g., paraffins,i-paraffins, naphthenes). Additionally, reactions in the hydroprocessingreactor 10 may cause a rupture of a bond of an organic compound,resulting in “cracking” of a hydrocarbon molecule into two or moresmaller hydrocarbon molecules, or resulting in a subsequent reactionand/or replacement of a heteroatom with hydrogen. Examples of reactionswhich may occur in the hydroprocessing reactor 10 include, but are notlimited to, the hydrogenation of olefins, removal of heteroatoms fromheteroatom-containing hydrocarbons (e.g., dechlorination), hydrocrackingof large paraffins or i-paraffins to smaller hydrocarbon molecules,hydrocracking of aromatic hydrocarbons to smaller cyclic or acyclichydrocarbons, conversion of one or more aromatic compounds to one ormore cycloparaffins, isomerization of one or more normal paraffins toone or more i-paraffins, selective ring opening of one or morecycloparaffins to one or more i-paraffins, or combinations thereof.

In embodiments, the hydroprocessing reactor 10 may be any vesselconfigured to contain the hydroprocessing catalyst disclosed herein. Thevessel may be configured for gas phase, liquid phase, vapor-liquidphase, or slurry phase operation. The hydroprocessing reactor 10 mayinclude one or more beds of the hydroprocessing catalyst in fixed bed,fluidized bed, moving bed, ebullated bed, slurry bed, or combinationsthereof, configuration. The hydroprocessing reactor 10 may be operatedadiabatically, isothermally, nonadiabatically, non-isothermally, orcombinations thereof. The reactions of this disclosure may be carriedout in a single stage or in multiple stages. For example, thehydroprocessing reactor 10 can be two reactor vessels fluidly connectedin series, each having one or more catalyst beds of the hydroprocessingcatalyst. Alternatively, two or more stages for hydroprocessing may becontained in a single reactor vessel. In embodiments having multiplestages, the first stage may dechlorinate and hydrogenate components ofthe hydrocarbon stream 1 to yield a first hydrocarbon product having afirst level of chloride compounds and olefins. The first hydrocarbonproduct may flow from the first stage to the second stage, where othercomponents of the first hydrocarbon product are dechlorinated andhydrogenated to yield a second hydrocarbon product stream (stream 2 inFIG. 1) having a second level of chloride compounds and olefins. Thesecond hydrocarbon stream may then be treated as described herein forstream 2.

In an embodiment, the hydroprocessing reactor 10 may comprise one ormore vessels.

In embodiments of a single vessel or multiple vessels, the sulphurpresent in the hydrocarbon stream 1 is removed as H₂S to provide areduced level of sulphur acceptable for downstream processing in steamcrackers and refinery units.

In an embodiment, hydrogen may feed to the hydroprocessing reactor 10 instream 8. The rate of hydrogen addition to the hydroprocessing reactor10 is generally sufficient to achieve the hydrogen-to-hydrocarbon ratiosdisclosed herein.

The disclosed hydroprocessing reactor 10 may operate at various processconditions. For example, contacting the hydrocarbon stream 1 with thehydroprocessing catalyst in the presence of hydrogen may occur in thehydroprocessing reactor 10 at a temperature of 100° C. to 450° C.;alternatively, 100° C. to 350° C.; or alternatively, 260° C. to 350° C.Contacting the hydrocarbon stream 1 with the hydroprocessing catalyst inthe presence of hydrogen may occur in the hydroprocessing reactor 10 ata pressure of 1 barg to 200 barg; or alternatively, 20 barg to 60 barg.Contacting the hydrocarbon stream 1 with the hydroprocessing catalyst inthe presence of hydrogen may occur in the hydroprocessing reactor 10 ata weight hourly space velocity (WHSV) of between 0.1 hr⁻¹ to 10 hr⁻¹; oralternatively, 1 hr⁻¹ to 3 hr⁻¹. Contacting the hydrocarbon stream 1with the hydroprocessing catalyst in the presence of hydrogen may occurin the hydroprocessing reactor 10 at a hydrogen-to-hydrocarbon (H₂/HC)flow ratio of 10 to 3,000 NL/L; or alternatively, 200 to 800 NL/L.

It is contemplated that dechlorination using the hydroprocessingcatalyst as described herein is performed in the hydroprocessing reactor10 without the use of chlorine sorbents, without addition of Na₂CO₃ inan effective amount to function as a dechlorinating agent, or both.

To prepare the hydrocracking catalyst, any hydroprocessing catalyst usedfor hydrogenation (e.g., saturation) of olefins and aromatichydrocarbons (e.g., a commercially available hydrotreating catalyst) maybe used. In an embodiment, the hydroprocessing catalyst is a cobalt andmolybdenum catalyst (Co—Mo catalyst) on an alumina support. In otherembodiments, the hydroprocessing catalyst is a nickel and molybdenumcatalyst (Ni—Mo catalyst) on an alumina support or tungsten andmolybdenum catalyst (W—Mo catalyst) on an alumina support. Othercatalyst embodiments may include platinum and palladium catalyst (Pt—Pdcatalyst) on an alumina support, nickel sulphides suitable for slurryprocessing, molybdenum sulphides suitable for slurry processing, nickeland molybdenum sulphides, or combinations thereof.

In embodiments where the hydrocarbon stream 1 comprises one or moresulphides and one or more chloride compounds, contacting the hydrocarboncarbon stream 1 with the hydroprocessing catalyst acts to activate thehydroprocessing catalyst by sulphiding and to acidify thehydroprocessing catalyst by chlorinating. Continuously contacting thehydroprocessing catalyst with the hydrocarbon stream 1 containing theone or more sulphides, the one or more chloride compounds, or both, maymaintain the catalyst activity on a continuous basis. Activating andmaintaining the activation of the hydroprocessing catalyst in effecttransforms the functionality of the hydroprocessing catalyst to alsoexhibit hydrocracking ability, e.g., the hydroprocessing catalysttransforms to a hydrocracking catalyst which maintains a hydrogenatingability.

In embodiments, the hydroprocessing catalyst is activated and/or theactivity is maintained by sulphiding the hydroprocessing catalystin-situ. For example, the hydroprocessing catalyst may be sulphided(i.e., activated) and/or sulphiding (i.e., maintaining the catalystactivity) of the hydroprocessing catalyst may be performed (e.g.,maintaining the hydroprocessing catalyst in sulphided form isaccomplished) by continuously contacting the hydrocarbon stream 1containing one or more sulphides compounds with the hydroprocessingcatalyst. The one or more sulphides may be included in the hydrocarbonstream 1 in an amount such that the sulphur content of the hydrocarbonstream 1 is about 0.5 wt %, 1 wt %, 1.5 wt %, 2 wt %, 2.5 wt %, 3 wt %,3.5 wt %, 4 wt %, 4.5 wt %, or 5 wt % based on the total weight of thehydrocarbon stream 1. In an embodiment, the sulphur content of thehydrocarbon stream 1 is up to about 3 wt % based on the total weight ofthe hydrocarbon stream 1.

Alternatively, the hydroprocessing catalyst may be sulphided (i.e.,activated) by contacting a catalyst activating stream 9 containing oneor more sulphides with the hydroprocessing catalyst for a period of time(e.g., 1, 2, 3, 4, 5, 6, 7, 8, 9, 10, 11, 12, 13, 14, 15, 16, 17, 18,19, 20, 21, 22, 23, 24, 25, 26, 27, 28, 29, 30 or fewer hours)sufficient to activate the hydroprocessing catalyst (before contactingthe hydrocarbon stream 1 with the hydroprocessing catalyst). In suchembodiments, the catalyst activating stream 9 may include a hydrocarboncarrier for the one or more sulphides, such as hexadecane. The one ormore sulphides may be included in the catalyst activating stream 9 in anamount such that the sulphur content of the catalyst activating stream 9is about 0.5 wt %, 1 wt %, 1.5 wt %, 2 wt %, 2.5 wt %, 3 wt %, 3.5 wt %,4 wt %, 4.5 wt %, 5 wt % or more based on the total weight of thecatalyst activating stream 9. In an embodiment, the sulphur content ofthe catalyst activating stream 9 is up to about 3 wt % based on thetotal weight of the catalyst activating stream 9. After thehydroprocessing catalyst is activated with the catalyst activatingstream 9, flow of the catalyst activating stream 9 may be discontinued,and sulphiding (i.e., maintaining the catalyst activity) of thehydroprocessing catalyst may be maintained (e.g., maintaining thehydroprocessing catalyst in sulphided form is accomplished) bycontinuously contacting the hydrocarbon stream 1 containing one or moresulphides with the hydroprocessing catalyst. The one or more sulphidesmay be included in the hydrocarbon stream 1 in an amount such that thesulphur content of the hydrocarbon stream 1 is about 0.5 wt %, 1 wt %,1.5 wt %, 2 wt %, 2.5 wt %, 3 wt %, 3.5 wt %, 4 wt %, 4.5 wt %, or 5 wt% based on the total weight of the hydrocarbon stream 1. In anembodiment, the sulphur content of the hydrocarbon stream 1 is up toabout 3 wt % based on the total weight of the hydrocarbon stream 1.

In embodiments, sulphiding and maintaining the catalyst in sulphidedform may use two different concentrations of sulphur content in thehydrocarbon stream 2. For example, the one or more sulphides may beincluded (e.g., provided via spiking stream 7) in the hydrocarbon stream2 in an amount such that the sulphur content of the hydrocarbon stream 1is about 2 wt % based on the total weight of the hydrocarbon stream 2for sulphiding, and the one or more sulphides may be maintained (e.g.,via spiking stream 7) in the hydrocarbon stream 2 in an amount such thatthe sulphur content of the hydrocarbon stream 1 is about 2 wt % based onthe total weight of the hydrocarbon stream 2 for maintaining thehydroprocessing catalyst in the sulphided form. In another example, theone or more sulphides may be included in the catalyst activating stream9 in an amount such that the sulphur content of the catalyst activatingstream 9 is about 3 wt % based on the total weight of the catalystactivating stream 9 for sulphiding, and the one or more sulphides may beincluded (e.g., via spiking stream 7) in the hydrocarbon stream 2 in anamount such that the sulphur content of the hydrocarbon stream 1 isabout 2 wt % based on the total weight of the hydrocarbon stream 2 formaintaining the hydroprocessing catalyst in the sulphided form.

In embodiments, catalyst activity is also maintained by chloriding thehydroprocessing catalyst. The hydroprocessing catalyst is chloridedusing the one or more chloride compounds provided to the hydroprocessingcatalyst by the hydrocarbon stream 1. The one or more chloride compoundswhich contribute to acidification of the hydroprocessing catalyst may beincluded in the hydrocarbon stream 1 in concentrations disclosed herein.

Sulphiding and maintaining the hydroprocessing catalyst in sulphidedform result in a catalyst which has hydrogenation sites (sulphidedmetal) for hydrogenation of components of the hydrocarbon stream 1.Chloriding the hydroprocessing catalyst results in a catalyst which hashydrocracking sites (chlorided alumina) for hydrocracking components ofthe hydrocarbon stream 1. That is, chloriding the hydroprocessingcatalyst transforms the catalyst into a hydrocracking catalyst (inaddition to having hydrogenation capabilities).

Due to hydrogenation reactions in the hydroprocessing reactor 10, inembodiments, the hydrocarbon product stream 2 may contain one or moreolefins in a concentration of less than 1 wt % based on the total weightof the hydrocarbon product stream 2. It is also contemplated that theconcentration of aromatic hydrocarbons in the hydrocarbon product stream2 is less than the concentration of aromatic hydrocarbons in thehydrocarbon stream 1 due to hydrogenation of at least a portion of thearomatic hydrocarbons in the hydroprocessing reactor 10. For example,aromatic hydrocarbons may be present in the hydrocarbon product stream 2in a concentration of less than 10, 9, 8, 7, 6, 5, 4, 3, 2, or 1 wt %based on the total weight of the hydrocarbon product stream 2.

The reaction product flows as effluent from the hydroprocessing reactor10 in the hydrocarbon product stream 2 to the separator 20. Separator 20may be any vessel which can recover a treated hydrocarbon stream 4 fromthe hydrocarbon product 2 which is fed to the separator 20. Inembodiments, the treated hydrocarbon stream 4 may be recovered byseparating a treated product (e.g., liquid product or gas product) fromsulphur and chlorine-containing gas in the separator 20, and flowing thetreated product in the treated hydrocarbon stream 4 from the separator20.

In an embodiment, the separator 20 is a condenser which operates atconditions which condense a portion of the hydrocarbon product stream 2into the treated product (e.g., liquid product or treated liquidproduct) while leaving sulphur and chlorine-containing compounds in thegas phase. The treated liquid product flows from the separator 20 intreated hydrocarbon stream 4, and the sulphur and chlorine-containinggas flows from the separator 20 via stream 3.

In another embodiment, the separator 20 is a scrubbing unit containing acaustic solution (e.g., a solution of sodium hydroxide in water) whichremoves (e.g., via reaction, adsorption, absorption, or combinationsthereof) sulphur and chlorine-containing gases from the hydrocarbonproduct stream 2 to yield the treated product (e.g., gas product ortreated gas product) which flows from the separator 20 via treatedhydrocarbon stream 4 while the sulphur and chlorine-containing compoundsin the gas phase flow from the separator 20 via stream 3.

In yet another embodiment, the separator 20 is a condenser incommunication with a scrubbing unit containing a caustic solution. Asdescribed above, the condenser may operate at conditions which condensea portion of the hydrocarbon product stream 2 into the mid-treatedproduct (e.g., liquid product or treated liquid product) while leavingsulphur and chlorine-containing compounds in the gas phase. Themid-treated liquid product flows from the condenser and experiences apressure reduction (e.g., via a valve or other pressure reducing deviceknown in the art with the aid of this disclosure) which creates aneffluent gas which flows from the scrubbing unit, leaving the treatedproduct flowing in treated hydrocarbon stream 4. Sulphur andchlorine-containing compounds flow from the separator 20 in stream 3.

In embodiments disclosed herein, no hydrogen halides and no halogenatedorganic compounds are recycled to the hydroprocessing reactor 10.

In embodiments, the treated hydrocarbon stream 4 includes one or morechloride compounds in a concentration of less than 5 ppm, 4 ppm, 3 ppm,2 ppm, 1 ppm, or 0.5 ppm based on a total weight of the treatedhydrocarbon stream 4. It is contemplated that the one or more chloridecompounds in the treated hydrocarbon stream 4 may be the same as some orall of the one or more chloride compounds in the hydrocarbon stream 1;alternatively, it is contemplated that only some of the one or morechloride compounds in the treated hydrocarbon stream 4 are the same asonly some of the one or more chloride compounds in the hydrocarbonstream 1; alternatively, it is contemplated that none of the one or morechloride compounds in the treated hydrocarbon stream 4 are the same asthe one or more chloride compounds in the hydrocarbon stream 1.

In additional embodiments, the treated hydrocarbon stream 4 includes theone or more olefins in a concentration which is less than aconcentration of the one or more olefins in the hydrocarbon stream 1 dueto hydrogenation of at least a portion of the one or more olefins fromthe hydrocarbon stream 1 while the hydrocarbon stream 1 is contactedwith the hydroprocessing catalyst in the hydroprocessing reactor 10. Inyet additional embodiments, the treated hydrocarbon stream 4 includesthe one or more olefins in a concentration which is less than aconcentration of the one or more olefins in the hydrocarbon stream 1 dueto hydrogenation and hydrocracking of at least a portion of the one ormore olefins from the hydrocarbon stream 1 while the hydrocarbon stream1 is contacted with the hydroprocessing catalyst in the hydroprocessingreactor 10. In an embodiment, the one or more olefins are present in thetreated hydrocarbon stream 4 in a concentration of less than 1 wt %based on the total weight of the treated hydrocarbon stream 4.

In embodiments, the treated hydrocarbon stream 4 includes one or moreparaffins, and the concentration of the one or more olefins is less than1 wt % based on the total weight of the treated hydrocarbon stream 4. Itis also contemplated that the concentration of aromatic hydrocarbons inthe treated hydrocarbon stream 4 is less than the concentration ofaromatic hydrocarbons in the hydrocarbon stream 1 due to hydrogenationof at least a portion of the aromatic hydrocarbons in thehydroprocessing reactor 10. For example, aromatic hydrocarbons may bepresent in the treated hydrocarbon stream 4 in a concentration of lessthan 10, 9, 8, 7, 6, 5, 4, 3, 2, or 1 wt % based on the total weight ofthe treated hydrocarbon product stream 4.

Due to hydrocracking of heavy hydrocarbon molecules when the hydrocarbonstream 1 is contacted with the hydroprocessing catalyst in thehydroprocessing reactor 10, the treated hydrocarbon stream 4 may have aboiling end point of 370° C. or less. A significant reduction inhydrocarbons boiling above 370° C. is obtained in stream 2 as comparedto hydrocarbon stream 1.

In embodiments where the treated hydrocarbon stream 4 includes one ormore chloride compounds in a concentration of less than 3 ppm, thetreated hydrocarbon stream 4 may be fed directly to the steam cracker30. In alternative embodiments where the treated hydrocarbon stream 4includes one or more chloride compounds in a concentration of 3 ppm ormore (e.g., 3 ppm to 5 ppm), the treated hydrocarbon stream 4 may beblended with a non-chlorinated hydrocarbon stream 5 to yield a blendedhydrocarbon stream 4′ (streams 4′ and 5 having dashed lines to denotethe alternative embodiment) having a concentration of one or morechlorides which is less than 3 ppm based on a total weight of theblended hydrocarbon stream 4′. The blended hydrocarbon stream 4′ may befed to the steam cracker 30.

Steam cracker 30 generally has feed specification requirements. First,the steam cracker 30 requires the concentration of chloride compounds inthe feed to the steam cracker 30 to be less than 3 ppm. Second, thesteam cracker 30 requires the concentration of olefins in a stream fedto the steam cracker 30 to be less than 1 wt %. Third, the steam cracker30 requires the boiling end point of the stream fed to the steam cracker30 to be 370° C. The steam cracker 30 cracks molecules or cleaves atelevated temperatures carbon-carbon bonds of the components in thetreated hydrocarbon stream 4 or blended hydrocarbon stream 4′ in thepresence of steam to yield high value products such as ethylene,propylene, butene, butadiene, aromatic compounds, or combinationsthereof. The high value products may flow from the steam cracker 30 viastream 6.

The disclosed hydrocracking catalyst prepared according to thetechniques disclosed herein both hydrocracks and hydrogenates componentsof a hydrocarbon stream fed to a hydroprocessing reactor 10 containingthe catalyst. Moreover, chloride compounds contained in the hydrocarbonstream are removed. In embodiments, simultaneous hydrogenation,dechlorination, and hydrocracking of a hydrocarbon stream components isachieved in a single hydroprocessing step using the hydrocrackingcatalyst prepared as disclosed herein, with the treated hydrocarbonproduct being capable of feeding to a steam cracker having the feedrequirements specified herein, without further separations orfractionations of the treated hydrocarbon product. Catalyst activity canbe initiated and/or maintained simultaneously with the simultaneoushydrogenation, dechlorination, and hydrocracking by using hydrocarbonstreams of the compositions disclosed herein which feed to ahydroprocessing reactor. The use of chloride compounds in thehydrocarbon stream 1 for activating and maintaining the activity of thehydrocracking catalyst in effect transforms the hydroprocessing catalystto a hydrocracking catalyst.

As is demonstrated in the examples below and discussed above, it hasbeen found that hydrocracking of olefins and heavy hydrocarbon moleculescontained in a hydrocarbon stream occurs using a hydrocracking catalystprepared using a hydroprocessing catalyst under the conditions disclosedherein. Hydrocracking according to the embodiments disclosed herein canoccur over the operating pressures disclosed herein for hydroprocessingreactor 10, including those low pressures demonstrated in the examples.Embodiments of the processes disclosed herein meet the boiling end pointof 370° C. required for steam crackers. Moreover, the disclosedembodiments demonstrate that about 30 wt % of the heavy hydrocarbonmolecules of a hydrocarbon stream can undergo hydrocracking at theconditions disclosed herein. When the hydrocarbon stream containsplastic pyrolysis oil, the heavier ends of the plastic pyrolysis oil arehydrocracked. Increased levels of paraffins due to the hydrocrackingability of the processes disclosed herein can result in a higherproduction of propylene in steam crackers. LPG gases are not liberatedin the disclosed processes until the temperature of the one or morecatalyst beds in the hydroprocessing reactor 10 reaches about 400° C.Liquid feed to crackers is maximized, and as a result, gas productformation is minimized, which is useful for existing plants which areconstrained on the gas flow rate to the gas compressor. In the disclosedembodiments, the production of methane and ethane is also low.

Dechlorination according to the embodiments disclosed herein can occurover the operating temperature ranges disclosed herein for thehydroprocessing reactor 10, including operating temperatures in thelow-end of the temperature ranges disclosed herein. Removal of chloridecompounds to less than 1 ppm occurs at temperatures below 350° C.Moreover, achieving sub-ppm chloride compound concentrations is possiblewith initial chloride content in the hydrocarbon stream 1 of 1,000 ppmor more. Moreover still, removal of chloride compounds is effective fordifferent types and classes of chlorides present in the hydrocarbonstream 1. When the hydroprocessing reaction is conducted at temperaturesat or above 350° C., it has been found that the treated hydrocarbonproduct contains 3 ppm or higher chloride content. In such cases, thetreated hydrocarbon product stream can be blended as described hereinwith a non-chlorinated stream 5 in such proportions to make the combinedblended hydrocarbon stream 4′ meet the steam cracker feedspecifications.

Operation at low temperatures (e.g., less than 350° C.) also has anadded advantage of corrosion mitigation of the reactor metallurgy. Formost metals and alloys used in the commercial reactors, corrosion ratesstart to increase at reactor temperatures over 300° C. It has been foundthat the efficiency of dechlorination according to the disclosedembodiments is good at reactor temperatures below 350° C., and thedechlorination process works with a sulphided Co—Mo catalyst on analumina support even as low as 260° C., with the chlorides in thetreated product being less than 1 ppm. Thus, the metallurgy corrosionissue is mitigated and longer equipment life is possible while achievingdechlorination to levels desirable for feed to steam cracker 30. Theprocesses disclosed herein have been demonstrated to work at pressuresas low as 20 barg, which is a less severe condition than the conditionstypically employed with a commercial hydrotreating catalyst. Ability tooperate at lower pressures reduces the required pressure rating forprocess vessels (e.g., the hydroprocessing reactor 10) and provides anopportunity for reduced investment costs.

The disclosed embodiments also demonstrate olefins in the hydrocarbonproduct are reduced typically to less than 1 wt % of the treatedhydrocarbon stream 4 from a feed olefin concentration of 20 wt % or morein the hydrocarbon stream 1.

Thus, the disclosed processes achieve the requirements of chloridecontent, olefin content, and boiling end point of the feed for a steamcracker simultaneously.

EXAMPLES

The subject matter having been generally described, the followingexamples are given as particular embodiments of the disclosure and todemonstrate the practice and advantages thereof. It is understood thatthe examples are given by way of illustration and are not intended tolimit the specification of the claims to follow in any manner.

Examples 1 to 6 were conducted in a fixed bed reactor located inside a3-zone split-tube furnace. The reactor internal diameter was 13.8 mm andhad concentrically located bed thermowell of 3 mm outer diameter. Thereactor was 48.6 cm long. Commercial hydroprocessing catalyst of Co—Moon alumina (8 g bone dry weight) was broken along the length toparticles of 1.5 mm long and diluted with SiC in the ratio of 60% SiC to40% catalyst to give a mean particle diameter of 0.34 mm. This was doneto avoid slip through of the chlorides due to wall slip or channeling inthe small diameter reactor. Pre-heating bed and post-catalyst inert bedswas provided in the form of 1 mm glass beads. The catalyst bedtemperature was controlled to isothermal by varying the controlledfurnace zone skin temperatures. The catalyst was sulphided using 3 wt %S in hexadecane (S was introduced as dimethyl disulphide). Liquid feed(i.e., the hydrocarbon stream) was fed through a metering pump and H₂gas was fed using a mass flow controller. The reactor effluent (i.e.,the hydrocarbon product) gases were cooled to condense out the liquids(i.e., the treated hydrocarbon stream in the form of a liquid product)under pressure while allowing non-condensed gases (e.g., containingchloride(s), chlorine, hydrogen sulphide, or combinations thereof) toseparate. Following liquid condensation, the pressure of the liquids wasreduced and effluent gas flow was scrubbed in a caustic scrubber andmeasured using a drum-type wet gas meter. The effluent gas flow wasanalyzed using a refinery gas analyzer (a custom gas analyzer from M/sAC Analyticals BV). The liquid product olefin content was determinedusing a Detailed Hydrocarbon Analyzer GC (DHA) and a boiling pointcharacterization was obtained using a SIMDIS GC. The liquid productchloride content was measured using a Chlora M-series analyzer(monochromatic wavelength dispersive X-ray Fluorescence technique, ASTMD7536).

Example 1

In Example 1, a hydrocarbon feed mixture was prepared by mixing 30 wt %n-hexadecane, 10 wt % i-octane, 20 wt % 1-decene, 20 wt % cyclohexane,and 20 wt % ethyl benzene. Dimethyl disulphide, 2-chloropentane,3-chloro-3-methyl pentane, 1-chlorohexane, (2-chloroethyl) benzene, andchlorobenzene were then added to give 205 ppm organic chlorides and asulphur content of 2 wt % S in the combined feed mixture. This combinedfeed mixture was used as the hydrocarbon stream which was contacted withthe hydroprocessing catalyst in the packed bed reactor as mentionedabove in the presence of H₂ at conditions of 280° C. reactortemperature, 60 barg reactor pressure, 0.92 hr⁻¹ WHSV, and 414 NL/LH₂/HC flow ratio. The liquid product (i.e., the treated hydrocarbonstream) was analyzed in a DHA wherein molecules lighter than C₁₃ areinjected into the GC column and heavier than C₁₃ are flushed out. Thenormalized composition of liquid product as measured by DHA wasparaffins (26.24 wt %), paraffins (17.28 wt %), olefins (0 wt %),naphthenes (33.61 wt %), and aromatics (22.88 wt %). SIMDIS analysis ofliquid product indicates that 78 wt % of the liquid product boils at180° C., and immediately at 79 wt %, the boiling point shifts to 286°C.; indicating that 22 wt % (i.e. 100−78=22) of the liquid product ishexadecane. This implies out of 30 wt % hexadecane in the feed(calculated based on the feed excluding chloride and sulphides, sincedimethyl disulphide is converted to gases, the chloride compounds aredechlorinated so as to contribute less than 0.5 wt % of the product), 8wt % of hexadecane was hydrocracked to lower products. As mentionedbefore, this 22 wt % does not get analyzed in DHA. This 22 wt %hexadecane unaccounted in DHA composition is added to the liquid productanalyzed by DHA (DHA composition multiplied by 0.78 fraction that wasinjected into DHA) and the resulting composition of the liquid productis 42.47 wt % paraffins, 13.48 wt % i-paraffins, 0 wt % olefins, 26.21wt % naphthenes and 17.84 wt % aromatics. In addition, the chloridecontent of the liquid product was 0.09 ppmw.

Example 1 demonstrates it is possible to simultaneously dechlorinate,hydrogenate, and hydrocrack a PIONA hydrocarbon stream containing heavyhydrocarbon molecules (e.g., hexadecane), a chloride content of morethan 200 ppm, and an olefin content of 20 wt % (calculated based on thefeed excluding chloride and sulphides) such that a portion of the heavyhydrocarbon molecules are hydrocracked, chloride content is reduced toless than 1 ppm, and olefins are completely removed (0 wt % in theliquid product). Comparing feed and liquid product compositions, it canbe said that paraffins, i-paraffins, and naphthenes have increased inconcentration, while aromatics have reduced in concentration and olefinswere completely depleted. This clearly indicates hydrocracking ofhexadecane as well as hydrocracking of olefins in feed. Thus, Example 1additionally demonstrates olefins are hydrocracked in addition to beinghydrogenated.

The DHA analysis summary by carbon number for the liquid product isshown below:

n-Paraffins, i-Paraffins, Olefins, Naphthenes, Aromatics, Total, CarbonNo. wt % wt % wt % wt % wt % wt % 2 3 4 0.015 0.015 5 0.012 0.012 60.016 0.18 27.136 0.048 27.217 7 0 8 0.145 14.226 0.547 21.979 36.896 90.079 5.901 0.834 6.814 10  26.01 2.93 0.039 11  12  Total, wt % 26.22117.268 35.584 22.86 99.933 Unknown 0.053 Heavies 0.013

Example 2

Example 2 explores the effect of operating pressure on hydrocrackingperformance. A hydrocarbon feed mixture was prepared by mixing 30 wt %n-hexadecane, 10 wt % i-octane, 20 wt % 1-decene, 20 wt % cyclohexane,and 20 wt % ethyl benzene. Dimethyl disulphide, 2-chloropentane,3-chloro-3-methyl pentane, 1-chlorohexane, (2-chloroethyl) benzene, andchlorobenzene were then added to give 205 ppm organic chlorides and asulphur content of 2 wt % S in the combined feed mixture. This combinedfeed mixture was used as a hydrocarbon stream which was contacted withthe sulphided hydroprocessing catalyst in the packed bed reactor asmentioned above in the presence of H₂ at conditions of 300° C. reactortemperature, 0.92 hr⁻¹ WHSV, and 414 NL/L H₂/HC flow ratio. Threedifferent pressure conditions were studied: 60 barg for Example 2A, 20barg for Example 2B, and 10 barg for Example 2C. The liquid products(i.e., the treated hydrocarbon streams) for each of Examples 2A to 2Cwere analyzed using SIMDIS, and the results are shown below:

Example 2A Example 2B Example 2C Liquid Product Liquid Product LiquidProduct 60 barg 20 barg 10 barg Cut, T, Cut, T, Cut, T, wt % ° C. wt % °C. wt % ° C. 0 61.4 0 52.0 0 61.4 5 72.0 5 61.4 5 72.0 10 72.0 10 72.010 72.0 15 72.0 15 72.0 15 72.0 20 72.0 20 72.0 20 72.0 25 72.0 25 72.025 72.0 30 87.6 30 72.0 30 72.0 35 87.6 35 72.0 35 87.6 40 87.6 40 87.640 87.6 45 87.6 45 87.6 45 132.0 50 87.6 50 134.6 50 137.2 55 129.4 55137.2 55 139.8 60 134.6 60 139.8 60 139.8 65 139.8 65 142.4 65 161.2 70170.6 70 163.2 70 173.8 75 176.0 75 175.4 75 177.0 79 177.6 80 179.0 78178.0 80 278.6 83 180.6 80 271.6 85 289.2 85 279.6 85 288.2 90 292.0 90291.0 90 291.6 95 294.0 95 294.6 95 294.0 99 295.4 99 296.8 99 295.4 100295.6 100 297.0 100 295.6

The DHA analysis summary of the liquid product boiling below 240° C. isshown below:

n- i- Example Paraffins, Paraffins, Olefins, Naphthenes, Aromatics,Unknown, Heavies, No. wt % wt % wt % wt % wt % wt % wt % 2A 22.50719.415 0.183 31.159 17.912 0.131 0.693 2B 19.544 21.513 0.047 30.49027.465 0.315 0.626 2C 21.368 21.281 0.000 24.687 30.719 0.355 1.591

The results provided in the tables above indicate that 20 wt % or lessof the liquid product for each of Examples 2A to 2C boils in thehexadecane boiling point range. In contrast, the feed contained 30 wt %hexadecane (calculated based on the feed excluding chlorides andsulphides). Hence, at all pressures, hydrocracking of heavy hydrocarbonmolecules (e.g., hexadecane) using a hydrogenation catalyst isdemonstrated.

The corresponding chloride contents of the liquid product (i.e., treatedhydrocarbon stream) at 60 barg, 20 barg, and 10 barg were respectively0.11 ppmw, 0.09 ppmw, and 0.12 ppmw.

The liquid product (analyzed in DHA) for Example 2A (60 barg) contained0.183 wt % olefins, for Example 2B (20 barg) contained 0.047 wt %, andfor Example 2C (10 barg) contained 0 wt % olefins. At lower pressures, asignificant increase in aromatics is observed.

Example 2 demonstrates it is possible to simultaneously dechlorinate andhydrocrack a PIONA hydrocarbon stream containing heavy hydrocarbonmolecules (e.g., hexadecane) and a chloride content of more than 200ppmw such that a portion of the heavy hydrocarbon molecules arehydrocracked and chloride content is reduced to less than 1 ppm for allpressures tested.

Example 3

In Example 3, a hydrocarbon feed mixture was prepared to contain 30 wt %n-hexadecane, 10 wt % i-octane, 20 wt % 1-decene, 20 wt % cyclohexaneand 20 wt % ethyl benzene. To this the organic chlorides mentioned inExample 2 above were added along with dimethyl disulphide to give 205ppm organic chlorides and 2 wt % S in the mixture. This feed was used asa hydrocarbon stream which was contacted with the sulphidedhydroprocessing catalyst in the packed bed reactor as mentioned above inthe presence of H₂ at conditions of 260° C. reactor temperature, 60 bargreactor pressure, 0.92 hr⁻¹ WHSV and 414 NL/L H₂/HC flow ratio. Theliquid product (i.e., the treated hydrocarbon stream) contained 0.1 ppmwchloride.

Example 3 demonstrates the effective removal of chloride compounds froma hydrocarbon stream at very low temperatures.

Example 4

In Example 4, a feed was prepared by mixing plastic pyrolysis oil (36.3g) with n-hexadecane (240 g), and then adding dimethyl disulphide (thesulphide) and 1-chlorohexane (the chloride compound) to give a sulphurcontent of 2.34 wt % and 836 ppm chloride in the feed. This feed wasused as a hydrocarbon stream which was contacted with thehydroprocessing catalyst in the packed bed reactor as mentioned above inthe presence of H₂ under several operating conditions as provided in thetable below:

T, P, WHSV, H₂/HC, Cl, ppm in ° C. barg hr⁻¹ NL/L liquid product 300 600.92 414 0.32 300 40 0.92 414 0.87 350 40 0.92 414 3.42 400 40 0.92 4143.15

The gas composition for the reactor effluents is shown below.

Cl, ppm n- i- T, P, WHSV, H₂/HC, in liquid H₂, CH₄, C₂H₆, C₃H₈, C₄H₁₀,C₄H₁₀, ° C. barg hr⁻¹ NL/L product mole % mole % mole % mole % mole %mole % 300 40 0.92 414 0.87 96.63 3.25 0.12 — — — 350 40 0.92 414 3.4295.32 4.48 0.2 — — — 400 40 0.92 414 3.15 93.96 5.21 0.45 0.23 0.08 0.07

As can be seen, the data indicates LPG gases are formed at temperaturesclose to 400° C.

Example 4 demonstrates it is possible to dechlorinate a hydrocarbonstream containing plastic pyrolysis oil and having chloride compoundsfrom a chloride content of more than 800 ppmw chlorides to less than 5ppmw in the liquid product. As can be seen from the above table, thechloride content of the liquid product (i.e., the treated hydrocarbonstream) increases when the reactor bed temperature is increased to at orabove 350° C. At temperatures below 350° C., Example 4 demonstratesremoval of chloride compounds to chloride contents less than 3 ppmw, andeven sub-ppm levels.

Example 5

In Example 5, a hydrocarbon feed mixture was prepared by mixing 30 wt %n-hexadecane, 10 wt % i-octane, 20 wt % 1-decene, 20 wt % cyclohexane,and 20 wt % ethyl benzene. Dimethyl disulphide, 2-chloropentane,3-chloro-3-methyl pentane, 1-chlorohexane, (2-chloroethyl) benzene, andchlorobenzene were then added to give 1100 ppm organic chlorides and asulphur content of 2 wt % S in the combined feed mixture. This combinedfeed mixture was used as the hydrocarbon stream which was contacted withthe hydrogenating catalyst in the packed bed reactor as mentioned abovein the presence of H₂ at conditions of 300° C. reactor temperature, 40barg reactor pressure, 0.92 hr⁻¹ WHSV, and 414 NL/L H₂/HC flow ratio.The liquid product contained 0.23 ppmw chlorides and paraffins of 22.569wt %, paraffins of 19.752 wt %, olefins of 0.114 wt %, naphthenes of33.242 wt %, aromatics of 23.7 wt %, unknowns of 0.16 wt % and heaviesof 0.463 wt % as per DHA analysis. This again demonstrates thedechlorination of liquid at much higher chloride concentrations.

The SIMDIS of liquid product resulted in the following distribution andalso indicated hydrocracking:

Cut, T, wt % ° C. 0 61.4 5 72 10 72 15 72 20 72 25 72 30 72 35 72 4087.6 45 87.6 50 132 55 134.6 60 137.2 65 142.4 70 170.6 75 175.4 80 17785 287 90 290 95 292.2 99 293.4 100 293.8

DHA Group type analysis of the liquid product by carbon number (in wt %)is as below:

n-Paraffins, i-Paraffins, Olefins, Naphthenes, Aromatics, Total, CarbonNo. wt % wt % wt % wt % wt % wt % 2 0 3 0 4 0.008 0.056 0.064 5 0.0330.021 0.054 6 0.035 0.05 26.925 0.072 27.082 7 0.013 0.008 0.012 0.033 80.287 13.892 0.951 21.97 37.1 9 0.172 0.114 5.265 1.623 7.174 10 22.1615.553 0.089 0.035 27.838 11 0.025 0.025 12 0.007 0.007 OxygenatesHeavies 0.464 Unknown 0.16 Total, wt % 100.001

In this example, the yield of liquid products was 95.5 wt % of the totalproducts. The balance was gas products.

Example 6

In Example 6, a n-hexadecane feed mixture was prepared by mixingn-hexadecane with dimethyl disulphide, 2-chloropentane,3-chloro-3-methyl pentane, 1-chlorohexane, (2-chloroethyl) benzene, andchlorobenzene to give 1,034 ppm of chlorides and 2 wt % Sulphur in thefeed. This combined feed mixture was used as the hydrocarbon streamwhich was contacted with the hydrogenating catalyst in the packed bedreactor as mentioned above in the presence of H₂ at conditions of 300°C. reactor temperature, 40 barg reactor pressure, 0.92 hr⁻¹ WHSV, and414 NL/L H₂/HC flow ratio. The liquid product contained 0.3 ppmwchlorides and paraffins of 22.569 wt %, i-paraffins of 19.752 wt %,olefins of 0.114 wt %, naphthenes of 33.242 wt %, aromatics of 23.7 wt%, unknowns of 0.16 wt % and heavies of 0.463 wt % as per DHA analysis.This again demonstrates the dechlorination of liquid at high chlorideconcentrations to sub-ppm levels.

The SIMDIS of liquid product resulted in the following distribution andalso indicated hydrocracking to the extent of about 15 wt % on achloride and sulphide-free feed basis:

Cut, T, wt % ° C. 0 61.4 5 129.4 10 161.2 13 170.6 14 260.2 15 272.4 20285.2 25 287.4 30 289 35 290.2 40 291.2 45 292.2 50 293 55 293.8 60294.4 65 295 70 295.6 75 296.2 80 297 85 297.4 90 297.8 95 298.2 99298.8 100 310.8

DHA Group type analysis of the liquid product by carbon number (in wt %)is as below and indicates conversion of n-hexadecane to various PIONAcomponents:

n-Paraffins, i-Paraffins, Olefins, Naphthenes, Aromatics, Total, CarbonNo. wt % wt % wt % wt % wt % wt % 2 0.005 0.005 3 0.006 0.006 4 0.0190.098 0.118 5 0.068 0.064 0.132 6 0.072 0.133 25.607 0.11 25.922 7 0.0160.034 0.051 8 0.401 13.31 1.268 21.179 36.157 9 0.133 0.136 5.53 2.4498.248 10 19.165 8.19 0.213 0.049 27.617 11 0.03 0.03 12 0.011 0.011Oxygenates Heavies 1.413 Unknown 0.29 Total, wt % 100

Example 7

Example 7 demonstrates a process for sulphiding a hydroprocessingcatalyst. The particular steps of the process are shown in FIG. 2. Thetime of 0 hours (zero time) in FIG. 2 corresponds to a time after thehydroprocessing catalyst is introduced into the hydroprocessing reactor.

At ambient temperature, the hydroprocessing reactor (having previouslybeen loaded with the hydroprocessing catalyst) was purged with hydrogenfor 30 to 60 minutes at a set operating pressure (e.g., 40 to 60 barg).The set operating pressure was maintained by venting the reactor whenthe pressure of the reactor during hydrogen purging increased above theset operating pressure (e.g., due to a hydrogen source pressure greaterthan the set operating pressure).

After purging the hydroprocessing reactor for 30-60 minutes at ambienttemperature, the hydrogen purge was stopped.

Still at the ambient temperature, the sulphiding feed was thenintroduced into the reactor using a high pressure pump against the setreactor pressure at a weight hourly space velocity (WHSV) of 3 hr⁻¹ (onbone-dry catalyst basis). The sulphiding feed (e.g., for use in dopingstream 7 of FIG. 1) was prepared by mixing n-hexadecane with dimethyldisulphide in appropriate quantity to give 3 wt % sulphur based on totalweight of the sulphiding feed. For the sulphiding feed, as per catalystsulphiding protocol followed, cracked feedstock cannot be used. Hence,n-hexadecane is used. In place of n-hexadecane, straight-run naphtha,diesel, or vacuum gas oils can also be used.

FIG. 2 indicates the hydroprocessing catalyst was soaked with asulphiding feed without a flow of hydrogen in the reactor and at ambienttemperature for a period of 3 hours (ending at time 3.5 hours after zerotime in FIG. 2). Catalyst soaking provides for complete wetting of thehydroprocessing catalyst; however, soaking is optional. Liquid wasdrained from the bottom of a downstream gas liquid separator.

After introducing the sulphiding feed to the reactor, thehydroprocessing reactor bed temperature was raised to 250° C. at a rateof 30° C. per hour with a flow of H₂ at a ratio of 200NL H₂/L liquidfeed. As shown in FIG. 2, the temperature was increased from a time of3.5 hours to a time of 10.8 hours after zero time.

The hydroprocessing reactor bed temperature was then held at 250° C. fora period of 8 hours. As shown in FIG. 2, the temperature was held from atime of 10.8 hours to a time of 18.8 hours after zero time.

After holding the bed temperature, the bed temperature was furtherincreased to 320° C. to 350° C. at a rate of 20° C. per hour without anytemperature overshoot at the final temperature. As shown in FIG. 2, thetemperature was increased from a time of 18.8 hours to a time of 22.3hours after zero time.

The hydroprocessing reactor bed temperature was then maintained at 320°C. to 350° C. for a period of 8 hours. As shown in FIG. 2, thetemperature was maintained at 320° C. to 350° C. from a time of 22.3hours to a time of 30.0 hours after zero time.

During the step of maintaining the temperature at 320° C. to 350° C. for8 hours, after 5 hours of maintaining the temperature at 320° C. to 350°C., gas sampling began, and a first gas sample was obtained from thereactor effluent. A second gas sample was obtained close to 8 hourswhile the bed temperature is maintained at 320° C. to 350° C. The firstand second gas samples were analyzed in a refinery gas analyzer (RGA)gas chromatograph and constancy of H₂S concentration in reactor effluentgases in the first and second samples signified further uptake ofsulphur on the catalyst did not take place. This marked the completionof the catalyst sulphiding process. If the first and second samples hadnot exhibited constancy in H₂S concentration, additional samples wouldhave been taken and the temperature maintained until two successivesamples exhibited constancy in H₂S concentration.

The present disclosure is further illustrated by the followingembodiments, which are not to be construed in any way as imposinglimitations upon the scope thereof. On the contrary, it is to be clearlyunderstood that resort can be had to various other aspects, embodiments,modifications, and equivalents thereof which, after reading thedescription herein, can be suggest to one of ordinary skill in the artwithout departing from the spirit of the present invention or the scopeof the appended claims.

Additional Disclosure

The following are enumerated embodiments which are provided asnon-limiting examples:

A first embodiment, which is a process for activating and maintaining acatalyst for use in hydrotreating a hydrocarbon stream to simultaneouslyreduce heavier boiling components, chlorides, and olefins, comprising:

continuously contacting the hydrocarbon stream with a hydroprocessingcatalyst in the presence of hydrogen, wherein the hydrocarbon streamcomprises one or more chloride compounds and one or more sulphides.

A second embodiment, which is the process of the first embodiment,wherein the one or more sulphides comprise dimethyl disulphide,mercaptans, carbon disulphide, hydrogen sulphide, or combinationsthereof.

A third embodiment, which is the process of any one of the first throughthe second embodiments, wherein the one or more sulfides of thehydrocarbon stream are present in an amount such that a sulphur contentof the hydrocarbon stream is about 0.5 wt % to about 5 wt % based on atotal weight of the hydrocarbon stream.

A fourth embodiment, which is the process of any of the first throughthe third embodiments, wherein the one or more sulfides of thehydrocarbon stream are present in an amount such that a sulphur contentof the hydrocarbon stream is about 2 wt % based on a total weight of thehydrocarbon stream.

A fifth embodiment, which is the process of any one of the first throughthe fourth embodiments, further comprising:

before the step of continuously contacting the hydrocarbon stream withthe hydroprocessing catalyst in the presence of hydrogen, contacting acatalyst activating stream with the hydroprocessing catalyst, whereinthe catalyst activating stream comprises one or more sulphides.

A sixth embodiment, which is the process of the fifth embodiment,wherein the catalyst activating stream further comprises one or morehydrocarbons.

A seventh embodiment, which is the process of the sixth embodiment,wherein the one or more hydrocarbons comprise hexadecane.

An eighth embodiment, which is the process of any one of the fifththrough the seventh embodiments, wherein the one or more sulfides of thecatalyst activating stream are present in an amount such that a sulphurcontent of the catalyst activating stream is about 0.5 wt % to about 5wt % based on a total weight of the catalyst activating stream.

A ninth embodiment, which is the process of any one of fifth through theeighth embodiments, wherein the one or more sulfides of the catalystactivating stream are present in an amount such that a sulphur contentof the catalyst activating stream is about 3 wt % based on a totalweight of the catalyst activating stream.

A tenth embodiment, which is the process of any one of the fifth throughthe ninth embodiments, wherein after the step of contacting and duringthe step of continuously contacting, the hydroprocessing catalyst hashydrogenation sites and hydrocracking sites.

An eleventh embodiment, which is the process of any one of the fifththrough the tenth embodiments, wherein the step of contacting a catalystactivating stream with the hydroprocessing catalyst is performed for aperiod of 30 hours or less, wherein the step of continuously contactinga hydrocarbon stream with a hydroprocessing catalyst initiates after theperiod elapses.

A twelfth embodiment, which is the process of any one of the fifththrough the eleventh embodiments, wherein the step of contacting acatalyst activating stream with the hydroprocessing catalyst isperformed ex-situ of a hydroprocessing reactor.

A thirteenth embodiment, which is the process of any one of the firstand the twelfth embodiments, wherein the step of continuously contactinga hydrocarbon stream with a hydroprocessing catalyst is performedex-situ of the hydroprocessing reactor.

A fourteenth embodiment, which is the process of any one of the fifththrough the thirteenth embodiments, wherein the step of contacting acatalyst activating stream with the hydroprocessing catalyst isperformed in-situ of a hydroprocessing reactor.

A fifteenth embodiment, which is the process of any one of the first andthe fourteenth embodiments, wherein the step of continuously contactinga hydrocarbon stream with a hydroprocessing catalyst is performedin-situ of the hydroprocessing reactor.

A sixteenth embodiment, which is the process of any one of the firstthrough the fifteenth embodiments, wherein the step of continuouslycontacting the hydrocarbon stream with the hydroprocessing catalyst isperformed at a temperature of 100° C. to 450° C.

A seventeenth embodiment, which is the process of any one of the firstthrough the sixteenth embodiments, wherein the step of continuouslycontacting the hydrocarbon stream with the hydroprocessing catalyst isperformed at a temperature of 100° C. to 350° C.

An eighteenth embodiment, which is the process of any one of the firstthrough the seventeenth embodiments, wherein the step of continuouslycontacting the hydrocarbon stream with the hydroprocessing catalyst isperformed at a temperature of 260° C. to 350° C.

A nineteenth embodiment, which is the process of any one of the firstthrough the eighteenth embodiments, wherein the step of continuouslycontacting the hydrocarbon stream with the hydroprocessing catalyst isperformed at a weight hourly space velocity of 0.1 to 10 hr⁻¹.

A twentieth embodiment, which is the process of any one of the firstthrough the nineteenth embodiments, wherein the step of continuouslycontacting the hydrocarbon stream with the hydroprocessing catalyst isperformed at a hydrogen to hydrocarbon ratio of 10 to 3,000 NL/L.

A twenty-first embodiment, which is the process of any one of the firstthrough the twentieth embodiments, wherein the step of continuouslycontacting the hydrocarbon stream with the hydroprocessing catalyst isperformed at a pressure of 1 to 200 barg.

A twenty-second embodiment, which is the process of any one of the firstthrough the twenty-first embodiments, wherein the hydrocarbon streamcomprises the one or more chloride compounds in a concentration ofgreater than 200 ppmw based on a total weight of the hydrocarbon stream.

A twenty-third embodiment, which is the process of any one of the firstthrough the twenty-second embodiments, wherein the hydrocarbon streamfurther comprises one or more olefins.

A twenty-fourth embodiment, which is the process of the twenty-thirdembodiment, wherein the one or more olefins are present in thehydrocarbon stream in a concentration of 20 wt % or more based on thetotal weight of the hydrocarbon stream.

A twenty-fifth embodiment, which is the process of any one of thetwenty-third through the twenty-fourth embodiments, wherein thehydrocarbon stream further comprises heavy hydrocarbon molecules,wherein the at least a portion of the one or more olefins comprises atleast a portion of the heavy hydrocarbon molecules.

A twenty-sixth embodiment, which is the process of any one of the firstor the twenty-third embodiment, wherein the hydrocarbon stream furthercomprises paraffins.

A twenty-seventh embodiment, which is the process of the twenty-sixthembodiment, wherein the hydrocarbon stream further comprises heavyhydrocarbon molecules, wherein the at least a portion of the one or moreparaffins comprises at least a portion of the heavy hydrocarbonmolecules.

A twenty-eighth embodiment, which is the process of any one of the firstthrough the twenty-seventh embodiments, wherein the hydrocarbon streamfurther comprises heavy hydrocarbon molecules.

A twenty-ninth embodiment, which is the process of the twenty-eighthembodiment, wherein a concentration of the heavy hydrocarbon moleculesin the hydrocarbon stream is 10 wt % to 90 wt % based on the totalweight of the hydrocarbon stream.

A thirtieth embodiment, which is the process of any of the twenty-fifthand twenty-seventh through the twenty-ninth embodiments, wherein theheavy hydrocarbon molecules comprise C₁₆ and larger hydrocarbons.

A thirty-first embodiment, which is the process of the thirtiethembodiment, wherein the C₁₆ and larger hydrocarbons comprise paraffins,i-paraffins, olefins, naphthenes, aromatic compounds, or combinationsthereof.

A thirty-second embodiment, which is the process of any one of the firstthrough the thirty-first embodiments, wherein the hydrocarbon stream isone or more of a plastic pyrolysis oil and a tire pyrolysis oil.

A thirty-third embodiment, which is the process of any one of the firstthrough the thirty-second embodiments, wherein the hydroprocessingcatalyst comprises cobalt and molybdenum on an alumina support, nickeland molybdenum on an alumina support, tungsten and molybdenum on analumina support, or nickel and molybdenum sulphides.

A thirty-fourth embodiment, which is the process of any one of the firstthrough the thirty-third embodiments, wherein the hydroprocessingcatalyst comprises platinum and palladium on an alumina support.

While embodiments of the disclosure have been shown and described,modifications thereof can be made without departing from the spirit andteachings of the invention. The embodiments and examples describedherein are exemplary only, and are not intended to be limiting. Manyvariations and modifications of the invention disclosed herein arepossible and are within the scope of the invention.

Accordingly, the scope of protection is not limited by the descriptionset out above but is only limited by the claims which follow, that scopeincluding all equivalents of the subject matter of the claims. Each andevery claim is incorporated into the specification as an embodiment ofthe present invention. Thus, the claims are a further description andare an addition to the detailed description of the present invention.The disclosures of all patents, patent applications, and publicationscited herein are hereby incorporated by reference.

What is claimed is:
 1. A process for activating and maintaining acatalyst for use in hydrotreating a hydrocarbon stream to simultaneouslyreduce heavier boiling components, chlorides, and olefins, comprising:continuously contacting the hydrocarbon stream with a hydroprocessingcatalyst in the presence of hydrogen, wherein the hydrocarbon streamcomprises one or more chloride compounds and one or more sulphides. 2.The process of claim 1, wherein the one or more sulphides comprisedimethyl disulphide, mercaptans, carbon disulphide, hydrogen sulphide,or combinations thereof.
 3. The process of claim 1, wherein the one ormore sulfides of the hydrocarbon stream are present in an amount suchthat a sulphur content of the hydrocarbon stream is about 0.5 wt % toabout 5 wt % based on a total weight of the hydrocarbon stream.
 4. Theprocess of claim 1, further comprising: before the step of continuouslycontacting the hydrocarbon stream with the hydroprocessing catalyst inthe presence of hydrogen, contacting a catalyst activating stream withthe hydroprocessing catalyst, wherein the catalyst activating streamcomprises one or more sulphides.
 5. The process of claim 4, wherein theone or more sulfides of the catalyst activating stream are present in anamount such that a sulphur content of the catalyst activating stream isabout 0.5 wt % to about 5 wt % based on a total weight of the catalystactivating stream.
 6. The process of claim 4, wherein after the step ofcontacting and during the step of continuously contacting, thehydroprocessing catalyst has hydrogenation sites and hydrocrackingsites.
 7. The process of claim 4, wherein the step of contacting acatalyst activating stream with the hydroprocessing catalyst isperformed for a period of 30 hours or less, wherein the step ofcontinuously contacting a hydrocarbon stream with a hydroprocessingcatalyst initiates after the period elapses.
 8. The process of claim 4,wherein the step of contacting a catalyst activating stream with thehydroprocessing catalyst is performed ex-situ of a hydroprocessingreactor.
 9. The process of claim 1, wherein the step of continuouslycontacting a hydrocarbon stream with a hydroprocessing catalyst isperformed ex-situ of the hydroprocessing reactor.
 10. The process ofclaim 4, wherein the step of contacting a catalyst activating streamwith the hydroprocessing catalyst is performed in-situ of ahydroprocessing reactor.
 11. The process of claim 1, wherein the step ofcontinuously contacting a hydrocarbon stream with a hydroprocessingcatalyst is performed in-situ of the hydroprocessing reactor.
 12. Theprocess of claim 1, wherein the step of continuously contacting thehydrocarbon stream with the hydroprocessing catalyst is performed at atemperature of 100° C. to 450° C.
 13. The process of claim 1, whereinthe step of continuously contacting the hydrocarbon stream with thehydroprocessing catalyst is performed at a weight hourly space velocityof 0.1 to 10 hr⁻¹, at a hydrogen to hydrocarbon ratio of 10 to 3,000NL/L, and at a pressure of 1 to 200 barg.
 14. The process of claim 1,wherein the hydrocarbon stream comprises the one or more chloridecompounds in a concentration of greater than 200 ppmw based on a totalweight of the hydrocarbon stream.
 15. The process of claim 1, whereinthe hydrocarbon stream further comprises one or more olefins, andwherein the one or more olefins are present in the hydrocarbon stream ina concentration of 20 wt % or more based on the total weight of thehydrocarbon stream.
 16. The process of claim 15, wherein the hydrocarbonstream further comprises heavy hydrocarbon molecules, wherein the atleast a portion of the one or more olefins comprises at least a portionof the heavy hydrocarbon molecules.
 17. The process of claim 1, whereinthe hydrocarbon stream further comprises paraffins.
 18. The process ofclaim 1, wherein the hydrocarbon stream further comprises heavyhydrocarbon molecules, and wherein a concentration of the heavyhydrocarbon molecules in the hydrocarbon stream is 10 wt % to 90 wt %based on the total weight of the hydrocarbon stream.
 19. The process ofclaim 1, wherein the hydroprocessing catalyst comprises cobalt andmolybdenum on an alumina support, nickel and molybdenum on an aluminasupport, tungsten and molybdenum on an alumina support, or nickel andmolybdenum sulphides.
 20. The process of claim 1, wherein thehydroprocessing catalyst comprises platinum and palladium on an aluminasupport.